JP6220121B2 - Azeotrope-like composition comprising 1-chloro-3,3,3-trifluoropropene - Google Patents

Description

  This application claims US application 12 / 605,609, filed October 26, 2009 (which claims the benefit of priority of US Provisional Application 61 / 109,007, filed October 28, 2008, and 2008 (Part of continuation (CIP) of US application 12 / 259,694, filed October 28, 1980). The contents of each of which are incorporated herein by reference in their entirety.

  The present invention relates generally to compositions comprising 1-chloro-3,3,3-trifluoropropene. More particularly, the present invention provides azeotrope-like compositions comprising 1-chloro-3,3,3-trifluoropropene and uses thereof.

  Fluorocarbon-based fluids such as chlorofluorocarbon (CFC) or hydrochlorofluorocarbon (HCFC) have desirable properties in industrial refrigerants, blowing agents, heat transfer media, solvents, gaseous dielectrics, and other applications. For these applications, single component fluids, or azeotrope-like mixtures, i.e. those that are not substantially fractionated by boiling and evaporation, are particularly desirable.

  Unfortunately, suspicious environmental problems such as global warming and ozone depletion are due to the use of some of these fluids, which currently limit their use. Hydrofluoroolefins (HFO) have been proposed as a possible alternative to such CFCs, HCFCs, and HFCs. However, locating new environmentally friendly non-fractionable mixtures containing HFO is difficult due to the fact that azeotrope formation cannot be easily predicted. Therefore, there is an ongoing search in the industry for new HFO-based mixtures that are acceptable and environmentally friendly alternatives to CFCs, HCFCs, and HFCs. The present invention satisfies these needs among others.

Applicants have 1-chloro-3,3,3-trifluoropropene and _{(HFO-1233zd), C 1} ~C 3 _alcohols, C 5 -C ₆ hydrocarbons, cyclopentene, 1-chloropropane, 2-chloropropane And an azeotrope by mixing with a second component selected from the group consisting of halogenated hydrocarbons selected from 1,1,1,3,3-pentafluorobutane, water, and optionally nitromethane It was found that a similar composition was formed. Preferred azeotrope-like mixtures of the present invention are used in multiple applications, such as as refrigerants, as blowing agents in the manufacture of insulating foams, as solvents in numerous cleanings, and in aerosols and other sprayable compositions, etc. Properties that are particularly desirable for other applications in In particular, Applicants tend to exhibit relatively low global warming potential (GWP) of these compositions, preferably less than about 1000, more preferably less than about 500, and even more preferably less than about 150. It was confirmed.

Accordingly, one aspect of the present invention, 1-chloro-3,3,3-trifluoropropene, and _C 1 -C _{3 alcohols,} C 5 -C ₆ hydrocarbons, cyclopentene, 1-chloropropane, 2-chloropropane, and A binary copolymer substantially consisting of a second component selected from the group consisting of a halogenated hydrocarbon selected from 1,1,1,3,3-pentafluorobutane, water, and optionally nitromethane. Includes compositions comprising a mixture that is a boiling mixture. In some preferred embodiments, the composition comprises: a co-foaming agent, a co-solvent, an active ingredient, and a lubricant, stabilizer, metal passivator, corrosion inhibitor, and flammable inhibitor. It further includes one or more of such additives. In some preferred embodiments, nitromethane is included in the mixture as a stabilizer. In some embodiments, nitromethane also contributes to the azeotrope-like properties of the composition.

  Other forms of the invention include at least about 15% by weight of the azeotrope-like mixtures described herein, and optionally co-foaming agents, fillers, vapor pressure modifiers, flame suppressants, and stabilizers. A foaming agent is provided.

Other aspects of the invention provide solvents for use in steam degreasing, cold cleaning, wiping, and similar solvent applications, including the azeotrope-like mixtures described herein.
Another aspect of the present invention provides a sprayable composition comprising an azeotrope-like mixture as described herein, an active ingredient, and optionally an inert ingredient and / or solvent, and an aerosol propellant. .

  Yet another aspect of the present invention is a polyurethane, polyisocyanurate, or phenol-based cell wall, as well as an azeotrope-like mixture as described herein disposed within at least a portion of the cell wall structure. A closed cell foam comprising a cellular gas is provided.

According to another aspect, there is provided a polyol premix comprising an azeotrope-like mixture as described herein.
According to another aspect, an effervescent composition is provided comprising an azeotrope-like mixture as described herein.

  According to another aspect, (a) adding a blowing agent comprising the azeotrope-like composition of claim 1 to a foamable mixture comprising a thermosetting resin; (b) reacting such foamable mixture. And (c) volatilizing such an azeotrope-like composition during such a reaction; and a method for producing a thermosetting foam is provided.

  According to another aspect, (a) adding a blowing agent comprising the azeotrope-like composition of claim 1 to a foamable mixture comprising a thermoplastic resin; (b) reacting such foamable mixture. Producing a thermoplastic foam; and (c) volatilizing such an azeotrope-like composition during such a reaction.

  According to another aspect, a thermoplastic foam is provided having a cellular wall comprising a thermoplastic polymer and a cellular gas comprising an azeotrope-like mixture as described herein. Preferably, the thermoplastic foam comprises a cellular gas having an azeotrope-like mixture as described herein, and is selected from polystyrene, polyethylene, polypropylene, polyvinyl chloride, polyethylene terephthalate, or combinations thereof. It has a cell wall composed of a polymer.

  According to another aspect, there is provided a thermosetting foam having a cellular wall comprising a thermosetting polymer and a cellular gas comprising an azeotrope-like mixture as described herein. Preferably, the thermoset foam is a cell gas having an azeotrope-like mixture as described herein, and a thermoset selected from polyurethane, polyisocyanurate, phenolic resin, epoxy resin, or combinations thereof. Includes a cell wall containing a polymer.

  In accordance with another aspect of the invention, there is provided a refrigerant comprising an azeotrope-like mixture as described herein.

In some aspects, the present invention is, HFO-1233zd, and _C 1 -C _{3 alcohols,} C 5 -C ₆ hydrocarbons, cyclopentene, 1-chloropropane, 2-chloropropane, and 1, 1, 1 An azeotrope-like composition comprising, preferably consisting essentially of, a halogenated hydrocarbon selected from 1,3-pentafluorobutane, nitromethane, or water. Thus, the present invention, in a preferred embodiment, is substantially free of CFC, HCFC, and HFC, has a very low global warming potential, a low ozone depletion potential, and a relatively constant boiling point. The above disadvantages are overcome by providing an azeotrope-like composition that exhibits properties.

  As used herein, the term “azeotrope-like” refers to a composition that is strictly azeotropic or generally behaves like an azeotropic mixture. An azeotropic mixture is a system of two or more components in which the composition of the liquid and the composition of the vapor are equal at a given pressure and temperature. In practice, this means that the components of the azeotropic mixture have a constant boiling point or a substantially constant boiling point and generally cannot be separated thermodynamically during the phase change. The composition of the vapor formed by boiling or evaporation of the azeotropic mixture is the same or substantially the same as the composition of the original liquid. Thus, the concentration of components in the liquid and vapor phases of an azeotrope-like composition changes minimally, if any, as the composition is boiled or otherwise evaporated. On the other hand, when the non-azeotropic mixture is boiled or evaporated, the concentration of components in the liquid phase changes to a considerable degree.

  As used herein with respect to components of an azeotrope-like composition, the term “substantially composed” means that the composition contains the indicated components in an azeotrope-like ratio, with additional components being new It means that additional components may be included if they do not form a boiling mixture-like system. For example, an azeotrope-like mixture consisting essentially of two types of compounds, provided that the additional components do not make the mixture non-azeotropic and do not form an azeotrope with either or both of the compounds. It forms a binary azeotrope that may optionally contain one or more additional components.

As used herein, the term “effective amount” refers to the amount of each ingredient that, when combined with other ingredients, forms the azeotrope-like composition of the invention.
Unless otherwise specified, the term HFO-1233zd means the cis isomer, trans isomer, or some mixture thereof.

  The term cis-HFO-1233zd as used herein with respect to components of an azeotrope-like mixture means that the amount of cis-HFO-1233zd relative to all isomers of HFO-1233zd in the azeotrope-like composition is It means at least about 95%, more preferably at least about 98%, even more preferably at least about 99%, even more preferably at least about 99.9%. In some preferred embodiments, the cis-HFO-1233zd component in the azeotrope-like composition of the present invention is substantially pure cis-HFO-1233zd.

  The term trans-HFO-1233zd as used herein with respect to components of an azeotrope-like mixture means that the amount of trans-HFO-1233zd relative to all isomers of HFO-1233zd in the azeotrope-like composition is It means at least about 95%, more preferably at least about 98%, even more preferably at least about 99%, even more preferably at least about 99.9%. In some preferred embodiments, the trans-HFO-1233zd component in the azeotrope-like composition of the present invention is substantially pure trans-HFO-1233zd.

  As used herein with respect to boiling point data, the term “atmospheric pressure” refers to the ambient pressure around the media concerned. Generally, the atmospheric pressure is 14.7 psia, but may vary by ± 0.5 psi.

  The azeotrope-like compositions of the present invention can be made by mixing an effective amount of HFO-1233zd, preferably with one or more other components in fluid form. Any of a wide variety of methods known in the art for mixing two or more components to form a composition can be adapted for use in the present method. For example, HFO-1233zd and methanol are blended, blended, or otherwise combined by hand and / or machine, as part of a batch or continuous reaction and / or process, or by a combination of two or more such steps. can do. In view of the disclosure herein, one of ordinary skill in the art will be able to readily produce an azeotrope-like composition according to the present invention without undue experimentation.

Fluoropropenes such as CF ₃ CCl═CH ₂ are described in US Pat. Nos. 2,889,379; 4,798,818; and 4,465,786, each of which is incorporated herein by reference. It has been such methods, may be prepared by known methods such as catalytic vapor phase fluorination of various saturated and unsaturated halogen-containing C ₃ compounds.

In EP-974,571 (also incorporated herein by reference), 1,1,1,3,3-pentafluoropropane (HFC-245fa) is added at a elevated temperature in the vapor phase with a chromium base. Of 1,1,1,3-chlorotrifluoropropene by contact with an alcohol solution of KOH, NaOH, Ca (OH) ₂ or Mg (OH) _{2 in} the liquid phase. ing. The final product is approximately 90% by weight trans isomer and 10% by weight cis. Preferably, the cis isomer is substantially separated from the trans form so that the resulting preferred form of 1-chloro-3,3,3-trifluoropropene is enriched in the cis isomer. Since the cis isomer has a boiling point of about 40 ° C. compared to the boiling point of the trans isomer of about 20 ° C., the two can be easily separated by any number of distillation methods known in the art. Can do. However, the preferred method is batch distillation. According to this method, a reboiler is charged with a mixture of cis and trans-1-chloro-3,3,3-trifluoropropene. The trans isomer is removed in the overhead stream and the cis isomer remains in the reboiler. The distillation can also be operated in a continuous distillation where the trans isomer is removed in the top stream and the cis isomer is removed in the bottom stream. This distillation process yields about 99.9 +% trans-1-chloro-3,3,3-trifluoropropene and 99.9 +% cis-1-chloro-3,3,3-trifluoropropene. Can be obtained.

In a preferred embodiment, the azeotrope-like composition comprises HFO-1233zd and _C 1 -C ₃ alcohol effective amount. _Preferably, C 1 -C ₃ alcohol is selected from methanol, ethanol, and from the group consisting of isopropanol. In some preferred embodiments, HFO-1233zd is trans-HFO-1233zd. In some other embodiments, HFO-1233zd is cis-HFO-1233zd.

An azeotrope-like composition of cis-HFO-1233zd / methanol:
In a preferred embodiment, the azeotrope-like composition comprises an effective amount of cis-HFO-1233zd and methanol. More preferably, these binary azeotrope-like compositions comprise about 78 to about 99.9% by weight cis-HFO-1233zd and about 0.1 to about 22% by weight methanol, more preferably about 85 To about 99.9 wt% cis-HFO-1233zd and about 0.1 to about 15 wt% methanol, even more preferably about 88 to about 99.5 wt% cis-HFO-1233zd and about 0.5 It is substantially composed of about 12% by weight methanol.

Preferably, the cis-HFO-1233zd / methanol composition of the present invention has a boiling point of about 35.2 ± 1 ° C. at ambient pressure (atmospheric pressure should be defined).
Trans-HFO-1233zd / methanol azeotrope-like composition:
In a preferred embodiment, the azeotrope-like composition comprises an effective amount of trans-HFO-1233zd and methanol. More preferably, these binary azeotrope-like compositions comprise about 70 to about 99.95% by weight trans-HFO-1233zd and about 0.05 to about 30% by weight methanol, more preferably about 90%. To about 99.95 wt% trans-HFO-1233zd and about 0.05 to about 10 wt% methanol, even more preferably about 95 to about 99.95 wt% trans-HFO-1233zd and about 0.05 wt%. Substantially composed of about 5% by weight of methanol.

  Preferably, the trans-HFO-1233zd / methanol compositions of the present invention are all measured at ambient pressure, from about 17 ° C to about 19 ° C, more preferably from about 17 ° C to about 18 ° C, and even more preferably about It has a boiling point of 17 ° C. to about 17.5 ° C., most preferably about 17.15 ° C. ± 1 ° C.

An azeotrope-like composition of cis-HFO-1233zd / ethanol:
In a preferred embodiment, the azeotrope-like composition comprises an effective amount of cis-HFO-1233zd and ethanol. More preferably, these binary azeotrope-like compositions comprise about 65 to about 99.9% by weight cis-HFO-1233zd and about 0.1 to about 35% by weight ethanol, more preferably about 79 To about 99.9% by weight cis-HFO-1233zd and about 0.1 to about 21% by weight ethanol, even more preferably from about 88 to about 99.5% by weight cis-HFO-1233zd and about 0.5%. Is substantially composed of ˜about 12 wt% ethanol.

Preferably, the cis-HFO-1233zd / ethanol composition of the present invention has a normal boiling point of about 37.4 ± 1 ° C. at ambient pressure.
Trans-HFO-1233zd / ethanol azeotrope-like composition:
In a preferred embodiment, the azeotrope-like composition comprises an effective amount of trans-HFO-1233zd and ethanol. More preferably, these binary azeotrope-like compositions comprise about 85 to about 99.9% by weight of trans-HFO-1233zd and about 0.1 to about 15% by weight of ethanol, more preferably about 92 To about 99.9 wt% trans-HFO-1233zd and about 0.1 to about 8 wt% ethanol, even more preferably about 96 to about 99.9 wt% trans-HFO-1233zd and about 0.1 Is substantially composed of about 4 wt% ethanol.

Preferably, the trans-HFO-1233zd / ethanol composition of the present invention has a normal boiling point of about 18.1 ± 1 ° C. at ambient pressure.
An azeotrope-like composition of cis-HFO-1233zd / isopropanol:
In a preferred embodiment, the azeotrope-like composition comprises an effective amount of cis-HFO-1233zd and isopropanol. More preferably, these binary azeotrope-like compositions are about 85 to about 99.99% by weight cis-HFO-1233zd and about 0.01 to about 15% by weight isopropanol, more preferably about 88%. To about 99.99% by weight cis-HFO-1233zd and about 0.01 to about 12% by weight isopropanol, even more preferably from about 92 to about 99.5% by weight cis-HFO-1233zd and about 0.5%. Substantially composed of about 8% by weight of isopropanol.

Preferably, the cis-HFO-1233zd / isopropanol composition of the present invention has a normal boiling point of about 38.1 ± 1 ° C. at ambient pressure.
Trans-HFO-1233zd / isopropanol azeotrope-like composition:
In a preferred embodiment, the azeotrope-like composition comprises an effective amount of trans-HFO-1233zd and isopropanol. More preferably, these binary azeotrope-like compositions comprise about 90 to about 99.9% by weight of trans-HFO-1233zd and about 0.1 to about 10% by weight of isopropanol, more preferably about 94. To about 99.9 wt% trans-HFO-1233zd and about 0.1 to about 6 wt% isopropanol, even more preferably about 95 to about 99.9 wt% trans-HFO-1233zd and about 0.1 Substantially composed of about 5% by weight of isopropanol.

Preferably, the trans-HFO-1233zd / isopropanol composition of the present invention has a normal boiling point of about 17.9 ° C. ± 1 ° C. at ambient pressure.
In a preferred embodiment, the azeotrope-like composition comprises HFO-1233zd and _C 5 -C ₆ hydrocarbons effective amount. _Preferably, C 5 -C ₆ hydrocarbons, n- pentane, isopentane, neopentane, cyclopentane, cyclopentene, is selected from the group consisting of n- hexane, and isohexane. In some preferred embodiments, HFO-1233zd is trans-HFO-1233zd. In some other embodiments, HFO-1233zd is cis-HFO-1233zd.

An azeotrope-like composition of trans-HFO-1233zd / n-pentane:
In a preferred embodiment, the azeotrope-like composition comprises an effective amount of trans-HFO-1233zd and n-pentane. More preferably, these binary azeotrope-like compositions comprise about 65 to about 99.95% by weight of trans-HFO-1233zd and about 0.05 to about 35% by weight of n-pentane, more preferably From about 84 to about 99.9% by weight trans-HFO-1233zd and from about 0.1 to about 16% by weight n-pentane, even more preferably from about 92 to about 99.5% by weight trans-HFO-1233zd and It is substantially composed of about 0.5 to about 8% by weight of n-pentane.

  Preferably, the trans-HFO-1233zd / n-pentane compositions of the present invention are all about 17 ° C. to about 19 ° C., more preferably about 17 ° C. to about 18 ° C., even more preferred, all measured at ambient pressure. Has a boiling point of about 17.3 ° C. to about 17.6 ° C., most preferably about 17.4 ° C. ± 1 ° C.

An azeotrope-like composition of cis-HFO-1233zd / n-pentane:
In a preferred embodiment, the azeotrope-like composition comprises an effective amount of cis-HFO-1233zd and n-pentane. More preferably, these binary azeotrope-like compositions comprise about 20 to about 99.5% by weight cis-HFO-1233zd and about 0.5 to about 80% by weight n-pentane, more preferably From about 50 to about 99.5 wt% cis-HFO-1233zd and from about 0.5 to about 50 wt% n-pentane, even more preferably from about 60 to about 99.5 wt% cis-HFO-1233zd and It is substantially composed of about 0.5 to about 40% by weight of n-pentane.

Preferably, the cis-HFO-1233zd / n-pentane composition of the present invention has a normal boiling point of about 35 ° C. ± 1 ° C. at ambient pressure.
Trans-HFO-1233zd / isopentane azeotrope-like composition:
In a preferred embodiment, the azeotrope-like composition comprises an effective amount of trans-HFO-1233zd and isopentane. More preferably, these binary azeotrope-like compositions are about 60 to about 99.95 wt.% Trans-HFO-1233zd and about 0.05 to about 40 wt.% Isopentane, more preferably about 70 From about 95% by weight trans-HFO-1233zd and from about 5 to about 30% by weight isopentane, even more preferably from about 80 to about 90% by weight trans-HFO-1233zd and from about 10 to about 20% by weight isopentane. It is substantially composed.

  Preferably, the trans-HFO-1233zd / isopentane compositions of the present invention are all measured at ambient pressure, from about 15 ° C to about 18 ° C, more preferably from about 16 ° C to about 17 ° C, and even more preferably about It has a boiling point of 16.7 ° C to about 16.9 ° C, most preferably about 16.8 ° C ± 1 ° C.

Trans-HFO-1233zd / neopentane azeotrope-like composition:
In a preferred embodiment, the azeotrope-like composition comprises an effective amount of trans-HFO-1233zd and neopentane. More preferably, these binary azeotrope-like compositions comprise about 5 to about 70 wt% trans-HFO-1233zd and about 30 to about 95 wt% neopentane, more preferably about 15 to about 55 wt%. % Trans-HFO-1233zd and from about 45 to about 85% by weight neopentane, even more preferably from about 20 to about 50% by weight trans-HFO-1233zd and from about 50 to about 80% by weight neopentane. Is done.

  Preferably, the trans-HFO-1233zd / neopentan compositions of the present invention are all measured at ambient pressure, from about 7.7 ° C to about 8.4 ° C, more preferably from about 7.7 ° C to about 8. It has a boiling point of 0 ° C., most preferably about 7.7 ° C. ± 1 ° C.

An azeotrope-like composition of cis-HFO-1233zd / neopentane:
In a preferred embodiment, the azeotrope-like composition comprises an effective amount of cis-HFO-1233zd and neopentane. More preferably, these binary azeotrope-like compositions comprise about 5 to about 50 wt% cis-HFO-1233zd and about 50 to about 95 wt% neopentane, more preferably about 20 to about 45 wt%. % Cis-HFO-1233zd and about 55 to about 80 wt% neopentane, even more preferably about 30 to about 40 wt% cis-HFO-1233zd and about 60 to about 70 wt% neopentane. Is done.

Preferably, the cis-HFO-1233zd / neopentan composition of the present invention has a normal boiling point of about 8 ° C. ± 1 ° C.
An azeotrope-like composition of trans-HFO-1233zd / cyclopentane:
In a preferred embodiment, the azeotrope-like composition comprises an effective amount of trans-HFO-1233zd and cyclopentane. More preferably, these binary azeotrope-like compositions comprise about 95 to about 99.9% by weight of trans-HFO-1233zd and about 0.1 to about 5% by weight of cyclopentane, more preferably about 97 to about 99.9 wt% trans-HFO-1233zd and about 0.1 to about 3 wt% cyclopentane, even more preferably about 98 to about 99.9 wt% trans-HFO-1233zd and about 2 Substantially consisting of up to about 98% by weight of cyclopentane.

Preferably, the trans-HFO-1233zd / cyclopentane composition of the present invention has a normal boiling point of about 17.5 ° C. ± 1 ° C. at ambient pressure.
An azeotrope-like composition of cis-HFO-1233zd / cyclopentane:
In a preferred embodiment, the azeotrope-like composition comprises an effective amount of cis-HFO-1233zd and cyclopentane. More preferably, these binary azeotrope-like compositions comprise from about 42 to about 99% by weight cis-HFO-1233zd and from about 1 to about 58% by weight cyclopentane, more preferably from about 50 to about 95%. Substantially from about 5% to about 50% by weight of cis-HFO-1233zd and even more preferably from about 60 to about 93% by weight of cis-HFO-1233zd and about 7 to about 40% by weight of cyclopentane. Constructed.

Preferably, the cis-HFO-1233zd / cyclopentane composition of the present invention has a normal boiling point of about 34.7 ° C. ± 1 ° C. at ambient pressure.
Trans-HFO-1233zd / cyclopentene azeotrope-like composition:
In a preferred embodiment, the azeotrope-like composition comprises an effective amount of trans-HFO-1233zd and cyclopentene. More preferably, these binary azeotrope-like compositions comprise about 95 to about 99.9% by weight trans-HFO-1233zd and about 0.1 to about 5% by weight cyclopentene, more preferably about 97 To about 99.9 wt% trans-HFO-1233zd and about 0.1 to about 3 wt% cyclopentene, even more preferably about 98 to about 99.9 wt% trans-HFO-1233zd and about 2 to about It consists essentially of 98% by weight of cyclopentene.

Preferably, the trans-HFO-1233zd / cyclopentene composition of the present invention has a normal boiling point of about 18.1 ± 1 ° C. at ambient pressure.
An azeotrope-like composition of trans-HFO-1233zd / n-hexane:
In a preferred embodiment, the azeotrope-like composition comprises an effective amount of trans-HFO-1233zd and n-hexane. More preferably, these binary azeotrope-like compositions comprise about 95 to about 99.99% by weight of trans-HFO-1233zd and about 0.01 to about 5% by weight of n-hexane, more preferably About 97 to about 99.99% by weight of trans-HFO-1233zd and about 0.01 to about 3% by weight of n-hexane, even more preferably about 97.2 to about 99.99% by weight of trans-HFO- 1233zd and about 0.01 to about 2.8% by weight n-hexane.

Preferably, the trans-HFO-1233zd / n-hexane composition of the present invention has a normal boiling point of about 17.4 ° C. ± 1 ° C. at ambient pressure.
An azeotrope-like composition of cis-HFO-1233zd / n-hexane:
In a preferred embodiment, the azeotrope-like composition comprises an effective amount of cis-HFO-1233zd and n-hexane. More preferably, these binary azeotrope-like compositions comprise about 80 to about 99.5% by weight cis-HFO-1233zd and about 0.5 to about 20% by weight n-hexane, more preferably From about 90 to about 99.5 wt% cis-HFO-1233zd and from about 0.5 to about 10 wt% n-hexane, even more preferably from about 95 to about 99.5 wt% cis-HFO-1233zd and It is substantially composed of about 0.5 to about 5% by weight of n-hexane.

Preferably, the cis-HFO-1233zd / n-hexane composition of the present invention has a normal boiling point of about 39 ° C. ± 1 ° C. at ambient pressure.
Trans-HFO-1233zd / isohexane azeotrope-like composition:
In a preferred embodiment, the azeotrope-like composition comprises an effective amount of trans-HFO-1233zd and isohexane. More preferably, these binary azeotrope-like compositions comprise from about 94.4 to about 99.99% by weight trans-HFO-1233zd and from about 0.01 to about 5.6% by weight isohexane, Preferably from 96% to about 99.99% by weight trans-HFO-1233zd and from about 0.01 to about 4% by weight isohexane, even more preferably from about 97 to about 99.99% by weight trans-HFO-1233zd. And from about 0.01 to about 3 weight percent isohexane.

  Preferably, the trans-HFO-1233zd / isohexane compositions of the present invention, all measured at ambient pressure, are from about 17 ° C to about 19 ° C, more preferably from about 17 ° C to about 18 ° C, and even more preferably about It has a boiling point of 17.3 ° C to about 17.6 ° C, most preferably about 17.4 ° C ± 1 ° C.

An azeotrope-like composition of cis-HFO-1233zd / isohexane:
In a preferred embodiment, the azeotrope-like composition comprises an effective amount of cis-HFO-1233zd and isohexane. More preferably, these binary azeotrope-like compositions comprise about 70 to about 99.5% by weight cis-HFO-1233zd and about 0.5 to about 30% by weight isohexane, more preferably 85 % To about 99.5% by weight cis-HFO-1233zd and about 0.5 to about 15% by weight isohexane, even more preferably from about 93 to about 99.5% by weight cis-HFO-1233zd and about 0%. From about 5 to about 7 weight percent isohexane.

Preferably, the cis-HFO-1233zd / isohexane composition of the present invention has a normal boiling point of about 37 ° C. ± 1 ° C.
In a preferred embodiment, the azeotrope-like composition comprises an effective amount of HFO-1233zd and a hydrohalocarbon. Preferably, the hydrohalocarbons are 1-chloropropane, 2-chloropropane, 1,1,1,3,3-pentafluorobutane (HFC-365mfc), and trans-1,2-dichloroethylene (trans-1,2- DCE). In some preferred embodiments, HFO-1233zd is trans-HFO-1233zd. In some other embodiments, HFO-1233zd is cis-HFO-1233zd.

Trans-HFO-1233zd / 1-chloropropane azeotrope-like composition:
In a preferred embodiment, the azeotrope-like composition comprises an effective amount of trans-HFO-1233zd and 1-chloropropane. More preferably, these binary azeotrope-like compositions comprise about 96 to about 99.9% by weight of trans-HFO-1233zd and about 0.1 to about 4% by weight of 1-chloropropane, more preferably About 98 to about 99.9% by weight of trans-HFO-1233zd and about 0.1 to about 2% by weight of 1-chloropropane, even more preferably about 99 to about 99.9% by weight of trans-HFO-1233zd and It is substantially composed of about 0.1 to about 1% by weight of 1-chloropropane.

Preferably, the trans-HFO-1233zd / 1-chloropropane composition of the present invention has a normal boiling point of about 18 ° C. ± 1 ° C. at ambient pressure.
Trans-HFO-1233zd / 2-chloropropane azeotrope-like composition:
In a preferred embodiment, the azeotrope-like composition comprises an effective amount of trans-HFO-1233zd and 2-chloropropane. More preferably, these binary azeotrope-like compositions comprise about 94 to about 99.9% by weight of trans-HFO-1233zd and about 0.1 to about 6% by weight of 2-chloropropane, more preferably About 97 to about 99.9% by weight of trans-HFO-1233zd and about 0.1 to about 3% by weight of 2-chloropropane, even more preferably about 99 to about 99.9% by weight of trans-HFO-1233zd and It is substantially composed of about 0.1 to about 1% by weight of 2-chloropropane.

Preferably, the trans-HFO-1233zd / 2-chloropropane composition of the present invention has a normal boiling point of about 17.8 ° C. ± 1 ° C. at ambient pressure.
Trans-HFO-1233zd / HFC-365mfc azeotrope-like composition:
In a preferred embodiment, the azeotrope-like composition comprises an effective amount of trans-HFO-1233zd and HFC-365mfc. More preferably, these binary azeotrope-like compositions comprise about 89 to about 99.9% by weight of trans-HFO-1233zd and about 0.1 to about 11% by weight of HFC-365mfc, more preferably About 92.5 to about 99.9% by weight of trans-HFO-1233zd and about 0.1 to about 7.5% by weight of HFC-365mfc, and even more preferably about 95 to about 99.9% by weight of trans- It consists essentially of HFO-1233zd and from about 0.1 to about 5% by weight of HFC-365mfc.

An azeotrope-like composition of trans-HFO-1233zd / trans-1,2-DCE:
In a preferred embodiment, the azeotrope-like composition comprises an effective amount of trans-HFO-1233zd and trans-1,2-DCE. More preferably, these binary azeotrope-like compositions comprise about 60 to about 99.99% by weight of trans-HFO-1233zd and about 0.01 to about 40% by weight of trans-1,2-DCE. More preferably from about 75 to about 99.99% by weight trans-HFO-1233zd and from about 0.01 to about 25% by weight trans-1,2-DCE, even more preferably from about 95% to about 99.%. Consists essentially of 99 wt% trans-HFO-1233zd and about 0.01 to about 5 wt% trans-1,2-DCE.

  Preferably, the composition of trans-HFO-1233zd / trans-1,2-DCE of the present invention is about 17 ° C. to about 19 ° C., more preferably about 17.5 ° C. It has a boiling point of 18.5 ° C, even more preferably from about 17.5 ° C to about 18 ° C, most preferably about 17.8 ° C ± 1 ° C.

An azeotrope-like composition of cis-HFO-1233zd / trans-1,2-DCE:
In a preferred embodiment, the azeotrope-like composition comprises an effective amount of cis-HFO-1233zd and trans-1,2-DCE. More preferably, these binary azeotrope-like compositions comprise about 42 to about 99.9% by weight cis-HFO-1233zd and about 0.1 to about 58% by weight trans-1,2-DCE. More preferably from about 55 to about 99.5% by weight cis-HFO-1233zd and from about 0.5 to about 45% by weight trans-1,2-DCE, even more preferably from about 65% to about 99% by weight. % Cis-HFO-1233zd and about 1 to about 35% by weight trans-1,2-DCE.

Preferably, the cis-HFO-1233zd / trans-1,2-DCE composition of the present invention has a boiling point of about 37.0 ° C. ± 1 ° C. at ambient pressure.
Trans-HFO-1233zd / methylal azeotrope-like composition:
In a preferred embodiment, the azeotrope-like composition comprises an effective amount of trans-HFO-1233zd and methylal. More preferably, these binary azeotrope-like compositions comprise about 95 to about 99.9 wt% trans-HFO-1233zd and about 0.1 to about 5 wt% methylal, more preferably about 97 To about 99.9 wt% trans-HFO-1233zd and about 0.1 to about 3 wt% methylal, even more preferably about 98.5 wt% to about 99.9 wt% trans-HFO-1233zd and It is substantially composed of about 0.1 to about 1.5 weight percent methylal.

Preferably, the trans-HFO-1233zd / methylal composition of the present invention has a normal boiling point of about 17.3 ± 1 ° C. at ambient pressure.
Trans-HFO-1233zd / methyl acetate azeotrope-like composition:
In a preferred embodiment, the azeotrope-like composition comprises an effective amount of trans-HFO-1233zd and methyl acetate. More preferably, these binary azeotrope-like compositions comprise about 90 to about 99.9% by weight of trans-HFO-1233zd and about 0.1 to about 10% by weight of methyl acetate, more preferably about 95 to about 99.9 wt% trans-HFO-1233zd and about 0.1 to about 5 wt% methyl acetate, even more preferably about 98.5 wt% to about 99.9 wt% trans-HFO- Consisting essentially of 1233zd and from about 0.1 to about 1.5 weight percent methyl acetate.

Preferably, the trans-HFO-1233zd / methyl acetate composition of the present invention has a normal boiling point of about 17.5 ° C. ± 1 ° C. at ambient pressure.
Trans-HFO-1233zd / water azeotrope-like composition:
In a preferred embodiment, the azeotrope-like composition comprises an effective amount of trans-HFO-1233zd and water. More preferably, these binary azeotrope-like compositions comprise about 70 to about 99.95 wt.% Trans-HFO-1233zd and about 0.05 to about 30 wt.% Water, more preferably about 86 To about 99.95 wt.% Trans-HFO-1233zd and about 0.05 to about 14 wt.% Water, most preferably about 90 to about 99.95 wt.% Trans-HFO-1233zd and about 0.05 to about It is substantially composed of about 10% by weight water.

Preferably, the trans-HFO-1233zd / water composition of the present invention has a boiling point of about 17.4 ° C. ± 1 ° C. at ambient pressure.
Trans-HFO-1233zd / nitromethane azeotrope-like composition:
In a preferred embodiment, the azeotrope-like composition comprises an effective amount of trans-HFO-1233zd and nitromethane. More preferably, these binary azeotrope-like compositions comprise about 98 to about 99.99% by weight trans-HFO-1233zd and about 0.01 to about 2% by weight nitromethane, more preferably about 99 To about 99.99% by weight of trans-HFO-1233zd and about 0.01 to about 1% by weight of nitromethane, even more preferably from about 99.9 to about 99.99% by weight of trans-HFO-1233zd and about 0. .01 to about 0.1% by weight nitromethane.

Preferably, the trans-HFO-1233zd / nitromethane composition of the present invention has a normal boiling point of about 17.4 ° C. ± 1 ° C. at ambient pressure.
An azeotrope-like composition of cis-HFO-1233zd / nitromethane:
In a preferred embodiment, the azeotrope-like composition comprises an effective amount of cis-HFO-1233zd and nitromethane. More preferably, these binary azeotrope-like compositions comprise about 95 to about 99.9% by weight cis-HFO-1233zd and about 0.1 to about 5% by weight nitromethane, more preferably about 97 To about 99.9 wt% cis-HFO-1233zd and about 0.1 to about 3 wt% nitromethane, even more preferably about 99 to about 99.9 wt% cis-HFO-1233zd and about 0.1 Substantially composed of about 1% by weight of nitromethane.

Preferably, the cis-HFO-1233zd / nitromethane composition of the present invention has a normal boiling point of about 39 ° C. ± 1 ° C. at ambient pressure.
An azeotrope-like composition of trans-HFO-1233zd / trans-1,2-DCE / methanol:
In a preferred embodiment, the azeotrope-like composition comprises an effective amount of trans-HFO-1233zd, methanol, and trans-1,2-DCE. More preferably, these ternary azeotrope-like compositions comprise about 80 to about 99.9% by weight trans-HFO-1233zd, about 0.05 to about 15% by weight methanol, and about 0.05 To about 10% by weight trans-1,2-DCE; even more preferably from about 90 to about 99.9% by weight trans-HFO-1233zd, from about 0.05 to about 9% by weight methanol, and from about 0. From about 5 to about 5 weight percent trans-1,2-DCE; most preferably from about 95 to about 99.9 weight percent trans-HFO-1233zd, from about 0.05 to about 5 weight percent methanol, and Consists essentially of 05 to about 3 wt% trans-1,2-DCE.

Preferably, the trans-HFO-1233zd / methanol / trans-1,2-DCE composition of the present invention has a boiling point of about 16.6 ° C. ± 1 ° C. at ambient pressure.
An azeotrope-like composition of trans-HFO-1233zd / methanol / n-pentane:
In a preferred embodiment, the azeotrope-like composition comprises an effective amount of trans-HFO-1233zd, methanol, and n-pentane. More preferably, these ternary azeotrope-like compositions comprise about 55 to about 99.90% by weight trans-HFO-1233zd, about 0.05 to about 10% by weight methanol, and about 0.05 To about 35% by weight n-pentane; even more preferably from about 79 to about 98% by weight trans-HFO-1233zd, from about 0.1 to about 5% by weight methanol, and from about 1.9 to about 16% by weight. N-pentane; most preferably from about 88 to about 96 wt% trans-HFO-1233zd, from about 0.5 to about 4 wt% methanol, and from about 3.5 to about 8 wt% n-pentane. It is substantially composed.

  Preferably, the trans-HFO-1233zd / methanol / n-pentane compositions of the present invention are all about 17 ° C to about 19 ° C, more preferably about 17 ° C to about 18 ° C, all measured at a pressure of about 14 psia. Even more preferably, it has a boiling point of about 17.1 ° C to about 17.6 ° C, most preferably about 17.4 ° C ± 1 ° C.

Trans-HFO-1233zd / n-pentane / trans-1,2-DCE azeotrope-like composition:
In a preferred embodiment, the azeotrope-like composition comprises an effective amount of trans-HFO-1233zd, n-pentane, and trans-1,2-DCE. More preferably, these ternary azeotrope-like compositions comprise about 85 to about 99.0% by weight of trans-HFO-1233zd, about 2.0 to about 4.5% by weight of n-pentane, and From about 0.01 to about 13% by weight of trans-1,2-DCE; even more preferably from about 88 to about 99% by weight of trans-HFO-1233zd, from about 3.0 to about 4.5% by weight of n- Pentane, and about 0.01 to about 9.0% by weight of trans-1,2-DCE; most preferably about 90 to about 96% by weight of trans-HFO-1233zd, about 3.7 to about 4.0% by weight. % N-pentane and from about 0.01 to about 6.3 wt% trans-1,2-DCE.

Preferably, the trans-HFO-1233zd / n-pentane / trans-1,2-DCE composition of the present invention has a boiling point of about 19 ° C. ± 1 ° C. at ambient pressure.
An azeotrope-like composition of cis-HFO-1233zd / isohexane / trans-1,2-DCE:
In a preferred embodiment, the azeotrope-like composition comprises an effective amount of cis-HFO-1233zd, isohexane, and trans-1,2-DCE. More preferably, these ternary azeotrope-like compositions comprise about 60 to about 80% by weight cis-HFO-1233zd, greater than 0 to about 20% by weight isohexane, and about 20 to about 35% by weight. Trans-1,2-DCE; even more preferably from about 62 to about 72% by weight cis-HFO-1233zd, from about 0.01 to about 13% by weight isohexane, and from about 25 to about 35% by weight trans- 1,2-DCE; most preferably from about 64.1 to about 70% by weight cis-HFO-1233zd, from about 0.01 to about 8.5% by weight isohexane, and from about 27.5 to about 30% by weight It is substantially composed of trans-1,2-DCE.

  Preferably, the cis-HFO-1233zd / isohexane / trans-1,2-DCE composition of the present invention has a boiling point of about 36.3 ° C. ± 1 ° C. at a pressure of about 767 mmHg.

An azeotrope-like composition of cis-HFO-1233zd / ethanol / trans-1,2-DCE:
In a preferred embodiment, the azeotrope-like composition comprises an effective amount of cis-HFO-1233zd, ethanol, and trans-1,2-DCE. More preferably, these ternary azeotrope-like compositions comprise about 60 to about 80% by weight cis-HFO-1233zd, greater than 0 to about 20% by weight ethanol, and about 20 to about 35% by weight. Trans-1,2-DCE; even more preferably from about 62 to about 72 weight percent cis-HFO-1233zd, from about 0.01 to about 13 weight percent ethanol, and from about 25 to about 35 weight percent trans- 1,2-DCE; most preferably from about 65 to about 70% by weight cis-HFO-1233zd, from about 0.01 to about 7.1% by weight ethanol, and from about 27.9 to about 30% by weight trans- It is substantially composed of 1,2-DCE.

  Preferably, the cis-HFO-1233zd / ethanol / trans-1,2-DCE composition of the present invention has a boiling point of about 35.8 ° C. ± 1 ° C. at a pressure of about 767 mmHg.

  The azeotrope-like composition of the present invention includes a variety of optional, including (but not limited to) lubricants, stabilizers, metal passivators, corrosion inhibitors, flammability inhibitors, and the like. Additives can be further included. Examples of suitable stabilizers include diene-based compounds and / or phenolic compounds and / or epoxides selected from the group consisting of aromatic epoxides, alkyl epoxides, alkenyl epoxides, and combinations of two or more thereof. It is done. Preferably, these optional additives do not affect the basic azeotrope-like properties of the composition.

Foaming agent:
In another aspect of the present invention, a blowing agent is provided comprising at least one azeotrope-like mixture as described herein. Polymer foams are generally of two general types: thermoplastic foams and thermoset foams.

  Thermoplastic foams are generally described in Throne, Thermoplastic Foams, 1996, Sherwood Publishers, Hinkley, Ohio or Klempner and Sendijarevic, Polymeric Foams and Foam Technology, 2nd edition 2004, Hander Gardner Publications, Inc., Cincinnati, OH. Manufactured by any method known in the art. For example, an extruded thermoplastic foam allows a solution of a blowing agent in a molten polymer that is formed in an extruder under pressure to pass through an orifice at ambient temperature or pressure, or possibly under reduced pressure to help the foam expand. It can be produced by an extrusion process that extrudes onto a moving belt. The blowing agent vaporizes and causes the polymer to expand. The polymer is simultaneously expanded and cooled under conditions that give it sufficient strength to maintain dimensional stability at the time corresponding to maximum expansion. Polymers used to make extruded thermoplastic foams include, but are not limited to, polystyrene, polyethylene (HDPE, LDPE, and LLDPE), polypropylene, polyethylene terephthalate, ethylene vinyl acetate, and mixtures thereof. In some cases, several additives including (but not limited to) nucleating agents (eg talc), flame retardants, colorants, processing aids (eg wax), crosslinking agents, permeability modifiers, etc. Is added to the molten polymer solution to optimize foam processing and properties. Further process steps such as irradiation to increase cross-linking, surface film lamination to improve foam skin quality, trimming and design to achieve foam dimension requirements, and other processes. It can also be included during the manufacturing process.

  In general, the blowing agent can include a wide range of amounts of the azeotrope-like composition of the present invention. However, it is generally preferred that the blowing agent comprises at least about 15% by weight blowing agent. In some preferred embodiments, the blowing agent comprises at least about 50% by weight of the composition, and in some embodiments, the blowing agent consists essentially of the azeotrope-like composition. In some preferred embodiments, the blowing agent, in addition to the azeotrope-like mixture, includes one or more azeotropes, fillers, vapor pressure modifiers, flame suppressants, stabilizers, and similar aids. Contains agents.

  In some preferred embodiments, the blowing agent is characterized as a physical (ie, volatile) blowing agent comprising the azeotrope-like mixture of the present invention. In general, the amount of blowing agent present in the blended mixture is determined by the desired foam density of the final foam product and the process pressure and solubility limits. For example, the proportion (parts by weight) of blowing agent may be within the range of about 1 to about 45 parts, more preferably about 4 to about 30 parts blowing agent per 100 parts by weight polymer. Blowing agents include chlorofluorocarbons such as trichlorofluoromethane (CFC-11), dichlorodifluoromethane (CFC-12), 1,1-dichloro-1-fluoroethane (CFC-12) mixed with an azeotrope-like composition. HCFC-141b), hydrochlorofluorocarbons such as 1-chloro-1,1-difluoroethane (HCFC-142b), chlorodifluoromethane (HCFC-22), 1,1,1,2-tetrafluoroethane (HFC-134a) ), 1,1-difluoroethane (HFC-152a), 1,1,1,3,3-pentafluoropropane (HFC-245fa), and 1,1,1,3,3-pentafluorobutane (HFC-365mfc) ) Hydrofluorocarbons such as propane, butane, isobutane, cyclopent Hydrocarbons such as emissions, carbon dioxide, chlorinated hydrocarbons, can be included alcohols, ethers, ketones, and additional components, such as mixtures thereof.

  In some embodiments, the blowing agent is characterized as a chemical blowing agent. A chemical blowing agent is a substance that decomposes upon exposure to temperature and pressure conditions in an extruder to generate a gas, generally carbon dioxide, carbon monoxide, nitrogen, hydrogen, ammonia, nitrous oxide, or mixtures thereof. . The amount of chemical blowing agent present depends on the desired final foam density. The proportion (in parts by weight) of the total chemical blowing agent blend may be in the range of less than 1 to about 15 parts, preferably from about 1 to about 10 parts blowing agent per 100 parts by weight polymer.

  In some preferred embodiments, dispersants, cell stabilizers, surfactants, and other additives can also be introduced into the blowing agent composition of the present invention. A surfactant is optional but is preferably added to act as a foam stabilizer. Some exemplary materials are DC-193, B-8404, and L-5340 (these are generally U.S. Pat. Nos. 2,834,748, 2,917,480, and 2,846,458 (each of these). Is sold under the name of a polysiloxane polyoxyalkylene block copolymer, such as those disclosed in (incorporated herein by reference). Other optional additives for the blowing agent mixture include tri (2-chloroethyl) phosphate, tri (2-chloropropyl) phosphate, tri (2,3-dibromopropyl) phosphate, tri (1,3- Flame retardants or inhibitors such as dichloropropyl) phosphate, diammonium phosphate, various halogenated aromatic compounds, antimony oxide, aluminum trihydrate, polyvinyl chloride and the like. For thermosetting foams, any thermosetting polymer can be used, generally including but not limited to polyurethane, polyisocyanurate, phenolic resin, epoxy resin, and combinations thereof. In general, these foams are one or more blowing agents comprising an azeotrope-like composition of the present invention, and optionally, cell stabilizers, solubility improvers, catalysts, flame retardants, auxiliary blowing agents, inert Manufactured by blending chemically reactive components in the presence of other additives including but not limited to fillers, dyes and the like. For the production of polyurethane or polyisocyanurate foam using the azeotrope-like composition described in the present invention, any method known in the art can be used. See Saunders and Frisch, Volumes I and II, Polyurethanes Chemistry and Technology (1962), John Wiley and Sons, New York, NY. Generally, polyurethane or polyisocyanurate foams are isocyanates, polyols or mixtures of polyols, blowing agents or mixtures of blowing agents, and catalysts, surfactants, and optionally flame retardants, colorants, or other Manufactured by blending other materials such as additives.

  It is advantageous in many applications to provide the ingredients for the polyurethane or polyisocyanurate foam in a pre-blended formulation. Most commonly, the foam formulation is pre-blended into two components. Isocyanates, and optionally some surfactants, and blowing agents constitute the first component, commonly referred to as the “A” component. The polyol or polyol mixture, surfactant, catalyst, blowing agent, flame retardant, and other isocyanate-reactive components constitute the second component, commonly referred to as the “B” component. Thus, polyurethane or polyisocyanurate foams are manually mixed for small quantities and preferably form blocks, slabs, laminates, in-situ injection panels and other components, spray-applied foams, foams, etc. It is easily manufactured by blending the A side and B side components by any of the mechanical mixing techniques. In some cases, other ingredients such as flame retardants, colorants, auxiliary blowing agents, water, and even other polyols can be added as a third stream to the mixing head or reaction site. Most conveniently, however, they are all contained in one B component as described above.

  Any organic polyisocyanate, including aliphatic and aromatic polyisocyanates, can be used in the synthesis of polyurethane or polyisocyanurate foams. Preferred as the type is an aromatic polyisocyanate. Typical aliphatic polyisocyanates are alkylene diisocyanates such as tri, tetra, and hexamethylene diisocyanate, isophorene diisocyanate, 4,4′-methylene bis (cyclohexyl isocyanate), and the like as typical aromatic polyisocyanates. M- and p-phenylene diisocyanate, polymethylene polyphenyl isocyanate, 2,4- and 2,6-toluene diisocyanate, dianisidine diisocyanate, bitoilene isocyanate, naphthylene-1,4-diisocyanate, bis (4-isocyanate) Natophenyl) methene, bis (2-methyl-4-isocyanatophenyl) methane and the like.

  Preferred polyisocyanates are polymethylene polyphenyl isocyanates, particularly mixtures comprising from about 30 to about 85% by weight of methylene bis (phenyl isocyanate), with the remainder of the mixture comprising a polymethylene polyphenyl polyisocyanate having a functionality greater than 2. .

  Typical polyols used in the production of polyurethane foams include aromatic amino-based polyethers such as those based on mixtures of 2,4- and 2,6-toluenediamine condensed with ethylene oxide and / or propylene oxide. Although a polyol is mentioned, it is not limited to these. These polyols have found utility in in situ injection molded foams. Other examples are aromatic alkylamino based polyether polyols such as those based on ethoxylated and / or propoxylated aminoethylated nonylphenol derivatives. These polyols generally find utility in spray-applied polyurethane foams. Other examples are sucrose-based polyols such as those based on sucrose derivatives condensed with ethylene oxide and / or propylene oxide and / or mixtures of sucrose and glycerol derivatives.

  Examples of polyols used in polyurethane modified polyisocyanurate foams include aromatic polyesters such as those based on complex mixtures of phthalate type or terephthalate type esters formed from polyols such as ethylene glycol, diethylene glycol, or propylene glycol. Although a polyol is mentioned, it is not limited to these. These polyols are used in rigid laminate materials and can be blended with other types of polyols, such as sucrose-based polyols, and used in other polyurethane foam applications as described above.

  Catalysts used in the production of polyurethane foams are typically N-alkylmorpholines, N-alkylalkanolamines, N, N-dialkylcyclohexylamines, and alkylamines (wherein the alkyl groups are methyl, ethyl, propyl, butyl, etc.) And tertiary amines such as, but not limited to, isomeric forms thereof; and heterocyclic amines. Representative but non-limiting examples are triethylenediamine, tetramethylethylenediamine, bis (2-dimethylaminoethyl) ether, triethylamine, tripropylamine, tributylamine, triamylamine, pyridine, quinoline, dimethylpiperazine, piperazine N, N-dimethylcyclohexylamine, N-ethylmorpholine, 2-methylpiperazine, N, N-dimethylethanolamine, tetramethylpropanediamine, methyltriethylenediamine, and the like, and mixtures thereof.

  In some cases, non-amine polyurethane catalysts are used. Typical examples of such catalysts are organometallic compounds such as bismuth, lead, tin, titanium, antimony, uranium, cadmium, cobalt, thorium, aluminum, mercury, zinc, nickel, cerium, molybdenum, vanadium, copper, manganese, and zirconium. is there. Representative examples include lead 2-ethylhexanoate, lead benzoate, ferric chloride, antimony trichloride, and antimony glycolate. Preferred organotin species include stannous salts of carboxylic acids such as stannous octoate, stannous 2-ethylhexanoate, stannous laurate, and the like, as well as dibutyltin diacetate, dibutyltin dilaurate, dioctyltin di Examples thereof include dialkyl tin salts of carboxylic acids such as acetate.

  In the production of polyisocyanurate foam, a trimerization catalyst is used for the purpose of converting the blend into a polyisocyanurate-polyurethane foam with an excess of component A. Trimerization catalysts used are known to those skilled in the art such as, but not limited to, glycerin salts and tertiary amine trimerization catalysts, and alkali metal carboxylates, and mixtures of various types of catalysts. It can be any catalyst. Preferred species within this class are potassium acetate, potassium octoate, and N- (2-hydroxy-5-nonylphenol) methyl-N-methylglycinate.

  Dispersants, foam stabilizers, and surfactants can be included in the blend. Surfactants are generally polysiloxane polyoxys such as those disclosed in U.S. Pat. Nos. 2,834,748, 2,917,480, and 2,846,458 (incorporated herein by reference). It is an alkylene block copolymer.

  Other optional additives for blending include tris (2-chloroethyl) phosphate, tris (2-chloropropyl) phosphate, tris (2,3-dibromopropyl) phosphate, tris (1,3-dichloropropyl) ) Flame retardants such as phosphate, diammonium phosphate, various halogenated aromatic compounds, antimony oxide, aluminum trihydrate, polyvinyl chloride and the like. Other optional components may include 0 to about 3% water, which chemically reacts with isocyanate to produce carbon dioxide. This carbon dioxide functions as an auxiliary blowing agent.

  The foaming agent or foaming agent blend disclosed in the present invention is also included in the mixture. Generally speaking, the amount of blowing agent present in the blended mixture will depend on the desired foam density of the final polyurethane or polyisocyanurate foam product. The proportion (parts by weight) of the total blowing agent blend may be in the range of 1 to about 45 parts, preferably about 4 to about 30 parts blowing agent per 100 parts polyol.

  The resulting polyurethane foam has a density of about 0.5 pounds / cubic foot to about 40 pounds / cubic foot, preferably about 1.0 to 20.0 pounds / cubic foot, and most preferably about 1.5 to 6.0. Can be in the pound / cubic foot range. The resulting density is a function of how much of the blowing agent or blowing agent mixture disclosed in the present invention is present in the A and / or B component or added at the time the foam is formed.

Foam and foamable composition:
Some aspects of the invention include a bubble wall based on polyurethane, polyisocyanurate, or phenolic resin, and a bubble gas disposed within at least a portion of the bubble, the bubble gas described herein. Including foams containing azeotrope-like mixtures. In some embodiments, the foam is an extruded thermoplastic foam. Preferred foams are from about 0.5 pounds / cubic foot to about 60 pounds / cubic foot, preferably from about 1.0 to 20.0 pounds / cubic foot, and most preferably from about 1.5 to 6.0 pounds / cubic foot. Having a density in the range of The density of the foam can be determined by how much blowing agent or blowing agent mixture (ie azeotrope-like mixture, as well as any auxiliary blowing agents such as carbon dioxide, chemical blowing agents, or other co-blowing agents). It is a function to make it exist in. These foams are generally rigid, but can be manufactured with varying degrees of flexibility to meet end use requirements. The foam may have a closed cell structure, an open cell structure, or a mixture of open and closed cells, with a closed cell structure being preferred. These foams are used in a variety of well-known applications such as but not limited to thermal insulation, floats, packaging, void filling, crafts and decorations, and shock absorption.

  In another aspect, the present invention provides a foamable composition. The foamable composition of the present invention generally has one or more components capable of forming foams such as polyurethane, polyisocyanurate, and phenolic resin-based compositions, and at least one of the types described herein. Including a blowing agent comprising an azeotrope-like mixture. In some embodiments, the foamable composition comprises a thermoplastic material, particularly a thermoplastic polymer and / or resin. Examples of thermoplastic foam components include polyolefins such as polystyrene (PS), polyethylene (PE), polypropylene (PP), and polyethylene terephthalate (PET), and foams formed therefrom, preferably low density foams. . In some embodiments, the thermoplastic foamable composition is an extrudable composition.

  In some embodiments, a method for manufacturing such a foam is provided. In particular, given the disclosure contained herein, one of ordinary skill in the art will recognize that the order and manner in which the foaming agent is formed and / or added to the foamable composition does not generally affect the feasibility of the invention. Will be done. For example, in the case of an extrudable foam, the various components of the blowing agent can be premixed. In some embodiments, the components of the foamable composition are not mixed prior to introduction into the extruder or added to the same location within the extruder. Thus, in some embodiments, it may be desirable to introduce one or more components of the blowing agent at a first location in the extruder that is upstream of the addition location of one or more other components of the blowing agent. Thus, the components are expected to be mixed and / or operated more effectively in the extruder. In some other embodiments, two or more components of the blowing agent are pre-blended and introduced together into the foamable composition. This is introduced directly or as part of the premix and then further added to the other part of the foamable composition.

Sprayable composition:
In a preferred embodiment, the azeotrope-like composition of the present invention can be used as a solvent in a sprayable composition alone or in combination with other known propellants. This solvent composition comprises the azeotrope-like composition of the present invention, more preferably consists essentially of it, and even more preferably consists of it. In some embodiments, the sprayable composition is an aerosol.

In some preferred embodiments, sprayable compositions are provided that include the above-described solvents, active ingredients, and optionally other ingredients such as inert ingredients, solvents, and the like.
Suitable spraying active materials include, without limitation, cosmetic materials such as deodorants, perfumes, hair sprays, cleaning solvents, lubricants, insecticides, and anti-asthma drugs. The term medicinal material is here meant in its broadest sense to encompass any and all materials that are effective or at least considered effective for therapy, diagnosis, analgesia, and similar treatments. This includes, for example, pharmaceuticals and biologically active substances.

Solvent and cleaning composition:
In other embodiments of the invention, the azeotrope-like compositions described herein can be used to wipe various soils such as mineral oil, rosin-based flux, silicone oil, lubricants, wiping, steam degreasing, Alternatively, it can be used as a solvent for washing and removing from various substrates by other means. In some preferred embodiments, the cleaning composition is an aerosol.

  The invention is further illustrated in the following examples, which are intended to be illustrative and not limiting in any way. For the related examples, a general type of boiling point instrument described by Swietolslowski in his book “Ebulliometric Measurements” (Reinhold, 1945) was used.

Example 1:
A boiling point measuring device having a condenser on the top and further comprising a vacuum jacketed tube fitted with a quartz thermometer or thermistor was used. About 10 cc of trans-HFO-1233zd was charged to the boiling point meter and then methanol was added in small increments measured. A temperature drop was observed when methanol was added, indicating that a binary minimum boiling azeotrope was formed. For methanol greater than 0 and up to about 51% by weight, the boiling point of the composition changes only below about 1.3 ° C. The boiling point of the binary mixtures shown in Table 1 changed only below about 0.02 ° C. Thus, the composition exhibited azeotrope and / or azeotrope-like properties over these ranges. To match the results, two boiling point instruments, one containing pure solvent and the other constructed with trans-HFO-1233zd, with the second component added as described above, were placed side by side. The temperature difference between the two was also measured.

Example 2:
A boiling point measuring device having a condenser on the top and further comprising a vacuum jacketed tube fitted with a quartz thermometer or thermistor was used. About 35 g of trans-HFO-1233zd was charged to the boiling point meter and then n-pentane was added in small increments measured. A temperature drop was observed when n-pentane was added to trans-HFO-1233zd, indicating that a binary minimum boiling azeotrope was formed. For n-pentane greater than 0 and up to about 30% by weight, the boiling point of the composition varies less than about 0.8 ° C. The boiling point of the binary mixtures shown in Table 2 changed only below about 0.02 ° C. Thus, the composition exhibited azeotrope and / or azeotrope-like properties over these ranges.

Example 3:
A boiling point measuring device having a condenser on the top and further comprising a vacuum jacketed tube fitted with a quartz thermometer or thermistor was used. About 17 g of trans-HFO-1233zd was charged to the boiling point meter and then isopentane was added in small increments measured. A drop in temperature was observed when isopentane was added to trans-HFO-1233zd, indicating that a binary minimum boiling azeotrope was formed. For isopentane greater than about 0 and up to about 30% by weight, the boiling point of the composition changed only below about 0.8 ° C. The boiling point of the binary mixtures shown in Table 3 changed only below about 0.2 ° C. Thus, the composition exhibited azeotrope and / or azeotrope-like properties over these ranges.

Example 4:
A boiling point measuring device having a condenser on the top and further comprising a vacuum jacketed tube fitted with a quartz thermometer or thermistor was used. About 17 g of neopentane was charged to the boiling point meter and then trans-HFO-1233zd was added in small increments measured. A temperature drop was observed when trans-HFO-1233zd was added to neopentane, indicating that a binary minimum boiling azeotrope was formed. As shown in Table 4, compositions containing about 19 to about 49 weight percent trans-HFO-1233zd had only a boiling point change of 0.1 ° C. or less. Thus, the composition exhibited azeotrope and / or azeotrope-like properties over at least these ranges.

Example 5:
A boiling point measuring device having a condenser on the top and further comprising a vacuum jacketed tube fitted with a quartz thermometer or thermistor was used. About 18 g of trans-HFO-1233 was charged to the boiling point instrument and then trans-1,2-DCE was added in small increments measured. A temperature drop was observed when trans-1,2-DCE was added to trans-HFO-1233, indicating that a binary minimum boiling azeotrope was formed. For trans-1,2-DCE greater than about 0.01 and up to about 53% by weight, the boiling point of the composition changed only below about 0.7 ° C. The boiling point of the binary mixtures shown in Table 4 changed only below about 0.3 ° C. Thus, the composition exhibited azeotrope and / or azeotrope-like properties over these ranges.

Examples 6-23:
For Examples 6-23, the basic procedure described in Examples 1-5 above was repeated. An azeotrope-like behavior was observed over a range of component concentrations, where the boiling point varied ≦ 1 ° C. The results are summarized below.

Example 24:
A boiling point measuring device comprising a condenser with a condenser on the top and a vacuum jacketed tube fitted with a quartz thermometer was used. About 10 cc of trans-HFO-1233zd was charged to the boiling point instrument and then nitromethane was added in small increments measured. A temperature drop was observed upon addition of nitromethane, indicating that a binary azeotrope-like composition was formed.

Example 25:
A boiling point measuring device comprising a condenser with a condenser on the top and a vacuum jacketed tube fitted with a quartz thermometer was used. About 10 cc of trans-HFO-1233zd was charged to the boiling point meter and then water was added in small increments measured. When water was added, a temperature drop was observed, indicating that a binary minimum boiling azeotrope was formed. For water greater than 0 and up to about 30% by weight, the boiling point of the composition varies by less than about 0.5 ° C. at ambient pressure.

Example 26:
A boiling point measuring instrument is used which consists of a vacuum jacketed tube with a condenser on top and a quartz thermometer. A predetermined amount of cis-HFO-1233zd is charged to the boiling point meter and then nitromethane is added in small increments measured. When adding nitromethane to cis-HFO-1233, a temperature drop is observed, indicating that a binary minimum boiling azeotrope is formed. The composition exhibits azeotrope and / or azeotrope-like properties over a range of about 95-99.9 wt% cis-HFO-1233zd and about 0.1 to about 5 wt% nitromethane. More obvious azeotrope and / or azeotrope-like properties occur over the range of about 97-99.9 wt% cis-1233zd and about 0.1 to about 3 wt% nitromethane; Even more evident over a range of .9 wt% cis-1233zd and about 0.1 to about 1 wt% nitromethane.

Example 27:
A boiling point measuring instrument is used which consists of a vacuum jacketed tube with a condenser on top and a quartz thermometer. A predetermined amount of cis-HFO-1233zd is charged to the boiling point instrument and then n-pentane is added in small increments measured. A temperature drop is observed when adding n-pentane to cis-HFO-1233, indicating that a binary minimum boiling azeotrope is formed. The composition exhibits azeotrope and / or azeotrope-like properties over a range of about 20-99.5 wt% cis-1233zd and about 0.5 to about 80 wt% n-pentane. More pronounced azeotrope and / or azeotrope-like properties occur over the range of about 50-99.5 wt% cis-1233zd and about 0.5 to about 50 wt% n-pentane; Even more evident over the range of ˜99.5 wt% cis-1233zd and about 0.5 to about 40 wt% n-pentane.

Example 28:
A boiling point measuring instrument is used which consists of a vacuum jacketed tube with a condenser on top and a quartz thermometer. A predetermined amount of cis-HFO-1233zd is charged to the boiling point meter and then neopentane is added in small measured increments. A temperature drop is observed when neopentane is added to cis-HFO-1233, indicating that a binary minimum boiling azeotrope is formed. The composition exhibits azeotrope and / or azeotrope-like properties over a range of about 5 to 50% by weight cis-1233zd and about 50 to about 95% by weight neopentane. More pronounced azeotrope and / or azeotrope-like properties occur over the range of about 20-45 wt% cis-1233zd and about 55 to about 80 wt% neopentane; about 30-40 wt% cis Even more evident over the range of -1233zd and about 60 to about 70 wt% neopentane.

Example 29:
A boiling point measuring instrument is used which consists of a vacuum jacketed tube with a condenser on top and a quartz thermometer. A predetermined amount of cis-HFO-1233zd is charged to the boiling point meter, and then n-hexane is added in small measured increments. When n-hexane is added to cis-HFO-1233, a temperature drop is observed, indicating that a binary minimum boiling azeotrope is formed. The composition exhibits azeotrope and / or azeotrope-like properties over a range of about 80-99.5 wt% cis-1233zd and about 0.5 to about 20 wt% n-hexane. More obvious azeotrope and / or azeotrope-like properties occur over the range of about 90-99.5 wt% cis-1233zd and about 0.5 to about 10 wt% n-hexane; Even more evident over the range of ˜99.5 wt% cis-1233zd and about 0.5 to about 5 wt% n-hexane.

Example 30:
A boiling point measuring instrument is used which consists of a vacuum jacketed tube with a condenser on top and a quartz thermometer. A predetermined amount of cis-HFO-1233zd is charged to the boiling point meter and then isohexane is added in small increments measured. A temperature drop was observed when isohexane was added to cis-HFO-1233, indicating that a binary minimum boiling azeotrope was formed. The composition exhibits azeotrope and / or azeotrope-like properties over a range of about 70-99.5 wt% cis-1233zd and about 0.5 to about 30 wt% isohexane. More obvious azeotrope and / or azeotrope-like properties occur over the range of about 85-99.5 wt% cis-1233zd and about 0.5 to about 15 wt% isohexane; Even more evident over the range of 5 wt% cis-1233zd and about 0.5 to about 7 wt% isohexane.

Example 31:
An azeotrope-like mixture containing 98% by weight trans-HFO-1233zd and about 2% by weight methanol is charged into an aerosol can. The aerosol valve is bent into place and HFC-134a is added through the valve to achieve a pressure in the can of about 20 psig. The mixture is then sprayed onto the surface, indicating that this azeotropic mixture is useful as an aerosol.

Examples 32-57:
For Examples 32-57, the process of Example 31 is generally repeated except that instead of trans-HFO-1233zd and methanol, an azeotrope-like mixture as shown in the table below is used. In some cases, the aerosol has a different co-aerosol or no co-aerosol, and in some cases consists of deodorants, perfumes, hair sprays, cleaning solvents, lubricants, pesticides, and pharmaceutical materials. Having at least one active ingredient selected from the group. Similar results are shown.

Example 58:
A mixture containing 98 wt% trans-HFO-1233zd and about 2 wt% methanol is loaded into an aerosol can. The aerosol valve is bent into place and HFC-134a is added through the valve to achieve a pressure in the can of about 20 psig. Next, the mixture is sprayed onto a metal piece soiled with solder flux. The flux is removed and the pieces are visually clean.

Examples 59-84:
For Examples 59-84, use azeotrope-like mixtures as shown in the table below instead of trans-HFO-1233zd and methanol, and use different azeosols instead of HFC-134a or no coaerosols. Others generally repeat the process of Example 58. In some cases, the method of applying the azeotropic mixture as a cleaning agent is vapor degreasing or wiping instead of spraying. In some cases, the azeotropic mixture detergent is applied neat. In some cases, the material to be cleaned was changed from solder flux to mineral oil, silicone oil, or other lubricants. Similar results are shown in each case.

Example 85:
A mixture containing 98% by weight trans-HFO-1233zd and 2% by weight methanol is prepared, the silicone oil is mixed with the blend, the solvent is allowed to evaporate, and a thin coating of silicone oil remains on the strip. This indicated that this solvent blend can be used for silicone oil deposition on various substrates.

Examples 86-111:
For Examples 85-111, the process of Example 85 is generally repeated except that trans-HFO-1233zd and methanol are used as an azeotrope-like mixture as shown in the table below.

Example 112:
A mixture containing 98 wt% trans-HFO-1233zd and 2 wt% methanol is prepared and the mineral oil is mixed with the blend. Mineral oil is evenly distributed throughout the blend. This showed that this azeotrope-like composition can be used as a solvent.

Examples 113-138:
For Examples 113-118, the procedure of Example 112 is generally repeated except that trans-HFO-1233zd and methanol are used as an azeotrope-like mixture as shown in the table below.

Example 139:
An azeotrope-like mixture of about 97% by weight trans-HFO-1233zd and about 3% by weight trans-1,2-DCE is prepared. This mixture is used as a blowing agent to produce closed cell polyurethane foam and closed cell polyisocyanate foam. Analysis of the foam gas of the resulting foam is required to contain at least a portion of an azeotrope-like mixture.

Examples 140-153:
For Examples 140-153, the procedure of Example 139 is generally repeated except that trans-HFO-1233zd and trans-1,2-DCE are used instead of the azeotrope-like mixtures shown in the table below.

Example 154:
A mixture containing 98 wt% trans-HFO-1233zd and 2 wt% methanol was prepared. Some stainless steel pieces were soiled with mineral oil. These pieces were then immersed in these solvent blends. Oil was removed in a short time by blending. When the piece was visually observed, it looked clean.

Examples 155-180:
For Examples 155-180, the process of Example 154 is generally repeated, except that trans-HFO-1233zd and methanol is used as an azeotrope-like mixture as shown in the table below.

Example 181:
A solvent blend was prepared containing 98 wt% trans-HFO-1233zd and 2 wt% methanol. Kester 1544 rosin solder flux was placed on a stainless steel strip and heated to about 300-400 ° F. This simulates contact with wave solder that is typically used to solder electronic components in the manufacture of printed circuit boards. The pieces were then immersed in the solvent mixture and removed without rinsing after about 15 seconds. The result indicates that the piece appeared clean by visual inspection.

Examples 182 to 207:
For Examples 185-207, the process of Example 181 is generally repeated except that trans-HFO-1233zd and methanol is used as an azeotrope-like mixture as shown in the table below.

Example 208:
A boiling point measuring device composed of a small flask equipped with an automatic dispenser and a condenser attached to the flask was used. The dispenser and condenser were cooled by a circulating bath. About 10 cc of a mixture of 96 wt% trans-1233zd and 4 wt% n-pentane was charged to the flask and trans-1,2-dichloroethylene was slowly added to the flask using an automatic dispenser. As shown in the table below, it was found that the boiling point of the mixture changed very slowly. The boiling point remained substantially constant at about 19 ° C., indicating that an azeotrope-like ternary mixture was formed.

Example 209:
A boiling point measuring device composed of a small flask equipped with an automatic dispenser and a condenser attached to the flask was used. The dispenser and condenser were cooled by a circulating bath. Approximately 10 cc of a mixture of 70 wt% cis-1233zd and 30 wt% trans-1,2-dichloroethylene was charged to the flask and isohexane was slowly added to the flask using an automatic dispenser. As shown in the table below, it was found that the boiling point of the mixture changed very slowly. The boiling point remained substantially constant at about 36.3 ° C., indicating that an azeotrope-like ternary mixture was formed.

Example 210:
A boiling point measuring device composed of a small flask equipped with an automatic dispenser and a condenser attached to the flask was used. The dispenser and condenser were cooled by a circulating bath. Approximately 10 cc of a mixture of 70 wt% cis-1233zd and 30 wt% trans-1,2-dichloroethylene was charged to the flask and ethanol was slowly added to the flask using an automatic dispenser. As shown in the table below, it was found that the boiling point of the mixture changed very slowly. The boiling point remained substantially constant at about 35.8 ° C., indicating that an azeotrope-like ternary mixture was formed.

  Thus, while a few specific aspects of the present invention have been described, various changes, modifications, and improvements will readily occur to those skilled in the art. Such alterations, modifications, and improvements, as will be apparent from this disclosure, are not expressly set forth herein but are intended to be part of this description and are within the spirit and scope of the invention. Intended. Accordingly, the foregoing description is by way of example only and is not intended as limiting. The invention is limited only as defined in the following claims and the equivalents thereto.

Claims (8)

  Trans-1-chloro-3,3,3-trifluoropropene in an amount of 79.9-95.0% by weight, n-pentane in an amount of 3.3-4.0% by weight, and 1.0-16 A ternary azeotrope-like mixture composed of trans-1,2-dichloroethylene in an amount of 8% by weight.   Cis-1-chloro-3,3,3-trifluoropropene in an amount of 64.1-69.6% by weight, isohexane in an amount of 0.5-8.5% by weight, and 27.5-29. A ternary azeotrope-like mixture composed of 8% by weight of trans-1,2-dichloroethylene.   Cis-1-chloro-3,3,3-trifluoropropene in an amount of 65.0-69.5% by weight, ethanol in an amount of 0.8-7.1% by weight, and 27.9-29. A ternary azeotrope-like mixture composed of 8% by weight of trans-1,2-dichloroethylene. A solvent composition comprising the ternary azeotrope-like mixture according to any one of claims 1 to 3 . A solvent for use in steam degreasing, cold cleaning, and / or wiping comprising the ternary azeotrope-like mixture according to any one of claims 1 to 3 . 6. A solvent according to claim 5 for cleaning soils such as mineral oil, rosin-based flux, silicone oil, lubricants from the substrate by wiping and / or steam degreasing. A cleaning composition comprising a ternary azeotrope-like mixture according to any one of claims 1 to 3 which is an aerosol. A sprayable composition comprising a solvent comprising a ternary azeotrope-like mixture according to any one of claims 1 to 3 , and optionally an inert component and / or solvent, and an aerosol propellant.